Gallium(III) sulfate explained

Gallium(III) sulfate refers to the chemical compound, a salt, with the formula Ga2(SO4)3, or its hydrates Ga2(SO4)3·xH2O. Gallium metal dissolves in sulfuric acid to form solutions containing [Ga(OH<sub>2</sub>)<sub>6</sub>]3+ and SO42− ions. The octadecahydrate Ga2(SO4)3·18H2O crystallises from these solutions at room temperature. This hydrate loses water in stages when heated, forming the anhydrate Ga2(SO4)3 above 150 °C[1] and completely above 310 °C. Anhydrous Ga2(SO4)3 is isostructural with iron(III) sulfate, crystallizing in the rhombohedral space group R.[2]

Preparation

Gallium(III) sulfate is prepared from the reaction of hydroxygallium diacetate and sulfuric acid. The two reactants were mixed at 90 °C and left for 2 days which produced the octadecahydrate. Then, it was dried in a vacuum for 2 hours which created the extremely hygroscopic anhydrous form. The overall reaction is below:

After the production, it was confirmed to be the simple salt, Ga2(SO4)3, by x-ray diffraction.[3]

Properties

When heated over 680 °C, gallium sulfate gives off sulfur trioxide, yielding gallium(III) oxide.A gallium sulfate solution in water mixed with zinc sulfate can precipitate ZnGa2O4.[4]

Derivatives

Basic gallium sulfate is known with the formula (H3O)Ga3(SO4)2(OH)6.[5]

Double gallium sulfates are known with composition NaGa3(SO4)2(OH)6, KGa3(SO4)2(OH)6, RbGa3(SO4)2(OH)6, NH4Ga3(SO4)2(OH)6. These compounds are isostructural with jarosite and alunite. Jarosite and alunite can contain a small amount of gallium substituted for iron or aluminium.[5] Organic base double gallium sulfates can contain different core structures, these can be chains of [Ga(SO<sub>4</sub>)<sub>3</sub>]3-, [Ga(OH)(SO<sub>4</sub>)<sub>2</sub>]2- or [Ga(H<sub>2</sub>O)<sub>2</sub>(SO<sub>4</sub>)<sub>2</sub>]− or sheets of [Ga(H<sub>2</sub>O)<sub>2</sub>(SO<sub>4</sub>)<sub>2</sub>]− units.[6]

formulamwcrystal
system		space
group		unit cell Åvolumedensitypropertiesreference
(H3O)Ga3(SO4)2(OH)6Rma=7.18 c=17.17 z=1.5766[7]
Ga4(OH)10SO4[8]
NH4Ga3(SO4)2(OH)6
trisodium gallium sulfateNa3Ga(SO4)3tetragonala = 9.451 c = 7.097[9]
NaGa3(SO4)2(OH)6
KGa3(SO4)2(OH)6
RbGa3(SO4)2(OH)6
Caesium gallium sulfate dodecahydrateCsGa(SO4)2•12H2OcubicPa3Z=42.127refractive index=1.461[10]
dimethylammonium gallium sulfate hexahydrate(CH3)2NH2Ga(SO4)2·6H2Oferroeelastic[11] [12]
guanidinium gallium sulfate[C(NH<sub>2</sub>)<sub>3</sub>]Ga(SO4)2·6H2OhexagonalP31ma=11.82 c=9.13ferroelectric[13]
Ethylenediammonium acid gallium sulfate[C<sub>2</sub>H<sub>10</sub>N<sub>2</sub>][H<sub>3</sub>O][Ga(SO<sub>4</sub>)<sub>3</sub>]
Ethylenediammonium basic gallium sulfate[C<sub>2</sub>H<sub>10</sub>N<sub>2</sub>][Ga(OH)(SO<sub>4</sub>)<sub>2</sub>]·H2O
Tetramethylenediammonium gallium sulfate[C<sub>4</sub>H<sub>14</sub>N<sub>2</sub>][Ga(H<sub>2</sub>O)<sub>2</sub>(SO<sub>4</sub>)<sub>2</sub>]2
Hexamethylenediammonium gallium sulfate[C<sub>6</sub>H<sub>18</sub>N<sub>2</sub>][Ga(H<sub>2</sub>O)<sub>2</sub>(SO<sub>4</sub>)<sub>2</sub>]2

Notes and References

  1. Book: 153 . A. J. Downs . Chemistry of Aluminium, Gallium, Indium and Thallium . Springer . 2012 . 9789401049603 .
  2. Contributions on the thermal behaviour of sulphates XVII.1 Single crystal structure refinements of In2(SO4)3 and Ga2(SO4)3 . M. . Krause . R. . Gruehn . . 1995 . 210 . 6 . 427–431 . 10.1524/zkri.1995.210.6.427 . 1995ZK....210..427K .
  3. V.Yu. Proydakova . S.V. Kuznetsov . V.V. Voronov . P.P. Fedorov . СИНТЕЗ СУЛЬФАТА ГАЛЛИЯ . Fine Chemical Technologies . 2017 . 12 . 3 . 52–57 . 10.32362/2410-6593-2017-12-3-52-57 . SYNTHESIS OF GALLIUM SULFATE . Russian. free .
  4. Hirano. Masanori. Okumura. Shiro. Hasegawa. Yasunori. Inagaki. Michio. October 2002. Direct Precipitation of Spinel-Type Zn(Fe, Ga)2O4 Solid Solutions from Aqueous Solutions at 90°C: Influence of Iron Valence of Starting Salt on Their Crystallite Growth. Journal of Solid State Chemistry. en. 168. 1. 5–10. 10.1006/jssc.2002.9662. 2002JSSCh.168....5H.
  5. Rudolph . Wolfram W. . Schmidt . Peer . Studies on synthetic galloalunites AGa3(SO4)2(OH)6: Synthesis, thermal analysis, and X-ray characterization . Thermochimica Acta . July 2011 . 521 . 1–2 . 112–120 . 10.1016/j.tca.2011.04.013 . 10.1.1.881.3389 .
  6. Kaufman. Elizabeth A.. Zeller. Matthias. Norquist. Alexander J.. 2010-10-06. A Slow Leak Synthetic Route to Organically Templated Gallium Sulfates. Crystal Growth & Design. en. 10. 10. 4656–4661. 10.1021/cg1009412. 1528-7483.
  7. Kydon. D. W.. Pintar. M.. Petch. H. E.. 1968-06-15. NMR Evidence of H 3 O + Ions in Gallium Sulfate. The Journal of Chemical Physics. en. 48. 12. 5348–5351. 10.1063/1.1668226. 1968JChPh..48.5348K. 0021-9606.
  8. Kang. Bong Kyun. Lim. Hyeong Dae. Mang. Sung Ryul. Song. Keun Man. Jung. Mong Kwon. Kim. Sang-Woo. Yoon. Dae Ho. 2015-01-20. Synthesis and Characterization of Monodispersed β-Ga 2 O 3 Nanospheres via Morphology Controlled Ga 4 (OH) 10 SO 4 Precursors. Langmuir. en. 31. 2. 833–838. 10.1021/la504209f. 25539482. 0743-7463.
  9. Fedorov. P. P.. Proidakova. V. Yu.. Kuznetsov. S. V.. Voronov. V. V.. November 2017. Phase equilibria in systems of gallium sulfate with lithium or sodium sulfate. Russian Journal of Inorganic Chemistry. en. 62. 11. 1508–1513. 10.1134/S0036023617110067. 103985885. 0036-0236.
  10. Web site: Howard E. Swanson, Nancy T. Gilfrich, Marlene I. Cook, Roger Stinchfield, and Paul C. Parks. 1 April 1959. Standard X-ray Diffraction Powder Patterns.
  11. Yasuda. Naohiko. Kaneda. Akio. Czapla. Zbigniew. March 1999. Pressure effects in dimethylammonium gallium sulfate (DMAGaS). Ferroelectrics. en. 223. 1. 71–78. 10.1080/00150199908260555. 1999Fer...223...71Y . 0015-0193.
  12. Völkel. G. Böttcher. R. Michel. D. Czapla. Z. Banys. J. 2005-07-20. Dimethylammonium gallium sulfate hexahydrate and dimethylammonium aluminium sulfate hexahydrate—members of a crystal family with exceptional commensurate/incommensurate phase sequences. Journal of Physics: Condensed Matter. 17. 28. 4511–4529. 10.1088/0953-8984/17/28/010. 2005JPCM...17.4511V. 98806133. 0953-8984.
  13. Geller. S.. Booth. D.P.. 1959-01-01. The crystal structure of guanidinium gallium sulfate hexahydrate, [C(NH2)3]Ga(SO4)2·6H2O]. Zeitschrift für Kristallographie - Crystalline Materials. 111. 1–6. 117–128. 10.1524/zkri.1959.111.16.117. 201840778. 2196-7105.

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